DK161771B - PROCEDURE FOR SOLUTION FRACTIONING OF FATS - Google Patents

Description

in

DK 161771 B

The invention relates to a process for the solution fractionation of animal or vegetable fats having a total content of saturated fatty acids of between 25-65%, especially butterfat and palm oil, in three well-defined fractions, the first fraction being a solid glyceride fraction having a melting point above 45 ° C, the second a semi-solid glyceride fraction similar to cocoa butter in terms of melting characteristics, the melting point of which is between 10 32-42 ° C, and the third fraction is an oil at room temperature, which can be used, for example, for cosmetic or pharmaceuticals. compositions.

These fractions are themselves useful in many food productions or in other productions, but they cannot be used alone. On the contrary, their usefulness can be greatly increased if they are mixed or mixed with other fats of animal or vegetable origin.

The process of the invention is characterized in that it consists of the following steps: a) dissolving the fat in a solvent, the solution ratio being from 1.5 to 7.5 ml. g of fat, and the solution is heated so much that complete solution is obtained, i.e. to approx. B) the solution of step a) is crystallized over 1-12 hours by slow cooling to ca. C) isolating a first precipitate formed in step b), which precipitates the heavy melt glyceride fraction having a melting point above 45 ° C, 30 d) washing out the first precipitate with a solvent which is cooled to a temperature at least 2 ° C lower than the crystallization temperature; e) crystallizing the filtrate from step c) for 1-12 hours, slowly lowering the temperature to 4-6 ° C, and dissolving the solution ratio; ) isolating another precipitate formed in steps

DK 161771B

2 e) which second precipitate is a semi-solid glyceride fraction whose melting point is between 32-42 ° C; g) leaching of the second precipitate with a solvent cooled to ca. And h) removing the solvent from the filtrate in step f) to obtain a third glyceride fraction, which is an oil at room temperature.

Herein, the method for fractionation of fats 10 in general, and butterfat and palm oil in particular, is disclosed by a combination of solution and temperature changes, thereby obtaining easily filterable fat crystals which can be readily isolated by decantation, centrifugation or vacuum filtration.

The method according to the invention can be carried out either portionwise or continuously, but the following examples only refer to the portioned execution of the method. The solvent used is of great importance for the fractional crystallization of fats, and according to the invention acetone is the preferred solvent. However, other solvents may also be used, provided that there is a corresponding change in the ratio of fat to solvent. Thus, in the process of the invention, solvents consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, mixed hydrocarbon solvents having a boiling point below 130 ° C, 1-nitropropane and 2-nitropropane, and various mixtures of these solvents can be used.

In the past, solution fractionation of fats, and especially butterfat, was carried out at very low temperatures, e.g. -55 ° C and -70 ° C, and at high dissolution conditions. Such fractionations were useful in the study of triglycerides, but no useful products were prepared in this way. In contrast, if beer is used,

DK 161771 B

The invention provides very moderate temperatures for crystallization of the fats and at the same time very low dissolution ratios, thus producing very useful and distinctive fractions.

Previous inventors and researchers have described the obtained products using classical analytical constants, such as the iodine number, capillary melting points, and saponification values. It is preferred here to characterize the products 10 according to the invention first and foremost by differential scanning calorimetry (DSC), whereby the product's melting process is graphically produced in the form of a melting profile as the product transfers from a solid to liquid form over a certain temperature range. Instead of specifying the unsaturation or molecular weight of the substances, a list of the fatty acids is set out herein with an indication of their molecular weight and unsaturation.

Danish Patent Specification No. 134,704 discloses a process for fractionating a fat material in which the fat material is dissolved in a solvent, the fraction or fractions being crystallized by cooling and a mixture of acetone and isopropyl alcohol used as the solvent.

Thus, the process of the invention does not merely consist of a choice of a fat and a solvent. The inventive method of the process lies in the instruction of special fats, special solvents and a special temperature control program, whereby new and very valuable fat fractions which cannot be prepared by other known methods can be prepared.

In addition, there are a number of fundamental differences between the prior art and Danish method of the present invention and the method according to the invention. According to Danish presentation no. 1344.704 is thus used exclusively

DK 161771 B

4 mixtures of acetone and isopropanol, whereas in the process of the invention only a single solvent is used, preferably acetone. The use of solvent mixtures is extremely impractical unless such a solvent is an azeotro mixture of constant composition and boiling point. Solvent recovery for recycling when the solvent is not an azeotropic mixture is not possible, since acetone and isopropyl alcohol cannot be completely separated by distillation. This makes recycling of the solvent used in the known process almost impossible, since a change in the composition of the solvent would change the nature of the fractionation and other characteristics. This disadvantage is completely avoided by the method according to the invention, where a single solvent is used and not a solvent mixture.

In the process known from Danish Patent Specification No. 134,704, a fat and solvent mixture in the weight ratio of 1: 2 to 2: 1 is used. In contrast, in the process of the invention, large amounts of solvent are used relative to the amount of fat, thereby achieving greater selectivity and fractions with specific and useful properties. Furthermore, the fat fractions obtained by the process according to the invention are precisely defined by Differential Scanning Calorimetry (DSC), which gives an absolutely graphic description of the melting properties of the fractions. Similarly, the exact chemical nature of the fractions is described by fatty acid component composition determined by gas chromatography. When comparing the DSC curves for fat fractions made by the process of the invention with the DSC curves for pure cocoa butter, it is clear that the melting properties are exactly the same. In contrast, the two fractions Sg and S3, which on pages 16-17 of Danish presentation no. 134,704 are compared with

DK 161771 B

5 cocoa butter, significantly different from cocoa butter. The indicated solid fat index values for fractions S2 and S3 do not correspond to the values for cocoa butter, since the S2 and 5 Sg solid fat index values are 9-13 units lower than the cocoa butter values at 10 ° C, 7-10 units lower at 21.1 ° C and 11-13 units higher at 33.3 ° C and thus these fractions are not cocoa butter-like materials. In contrast, the DSC data indicated shows a complete and accurate coincidence of the melting properties of the fat fraction produced by the process of the invention and cocoa butter.

However, although it is known from Danish Patent Specification No. 134,704 to fractionate palm oil, the obtained fractions differ substantially from the fractions obtained by the process of the invention. Furthermore, the agents used in the process of the invention are substantially different from the agents used in the known method. In addition, the fractions obtained by the process 20 according to the invention are described completely by exact scientific methodology, which is not the case with the fractions prepared by the method according to Danish Patent Specification No. 1344.704.

It has been found that the only limiting factor of the process of the invention is the content of saturated fatty acid in the fat to be fractionated. A fat which must be fractionated by the process of the invention must have a total content of saturated fatty acids of not less than 25% and not more than 65%. Furthermore, the saturated fatty acids must be mainly a mixture of palmitic acid (16 carbon atoms) and stearic acid (18 carbon atoms), and the unsaturated fatty acids must be mainly oleic acid (18 carbon atoms, monounsaturated). The following Table 35 lists a number of fats which can be successfully fractionated by the process of the invention.

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6

List of Fats Suitable for Solution Fractionation ______

J

t, ,,,, Palmitin- Stearin-. . , 1

Feature £ Acid (C-16) Acid (C-18) Total J

5 cocoa butter 27 33 60

Borneo tallow 5 42 47

Chinese vegetable cc 0 CQ

fat 66 2 68 Indian butter 55 5 60 10 Illepe butter 25 25 50

Siak tallow 8 55 63

Kokum butter 5 50 55

Gamboze butter 8 42 50 j

Sierra Leone c co η r ·. 6 46 52 15 butter

Malabar tallow 10 40 50 palm oil 47 4 51

Piqui fat 46 4 50

Rambutin tallow 2 45 47 20 beef fat 26 14 40 camel fat 31 31 62 chicken fat 27 7 34 deer fat 24 31 55 hippo fat 27 21 48 25 horse fat 27 6 33 pig fat 28 15 43 sheep fat 24 13 37 goat milk fat 28 6 34

Menhaden fat 29 4 33 30 mackerel fat 28 4 32

The most profitable sources of these fats and the most recognized in all cultures for food production are butterfat and palm oil. It is therefore preferred to describe in detail the solution fractionation of butterfat and of palm oil.

In accordance with the invention, the melted butter fat is dissolved in acetone,

7 DK 161771B

what is used is a solution ratio ranging from 1.5 to 7.5 milliliters of acetone per liter. grams of fat. The solution is heated to approx. 45 ° C to ensure complete dissolution. The solution is then allowed to cool slowly down to the initial crystallization temperature of 14-16 ° C. The cooling can be done in a variety of ways, with or without mechanical stirring. The crystallizer may be located in a thermostat compartment or it may be provided with suitable cooling tubes.

Moderate stirring will speed up the process. If no agitation is used, the crystallization process is allowed to continue until no further precipitation occurs, which usually lasts from 6-12 hours. If the crystallizer is provided with a vane-type stirrer that rotates between 35 and 70 rpm. per minute, the crystallization equilibrium will be reached in less than two hours. The precipitate can then be isolated by filtration, either by vacuum or pressure, by centrifugation or by decanting the overlying clear filtrate. In all cases, the isolated precipitate should be washed out with cold acetone in an amount equal to about 10% of the original amount and at a temperature at least 2 ° C lower than the crystallization temperature.

An alternative method is to allow the sediment to accumulate and to remove the overlying liquid by decanting or switching. The acetone for leaching can be added and removed in the same way, thus eliminating the need to filter. The more efficient the leaching, the cleaner the crystalline product becomes.

Using effective precipitates, only two crystallizations are required to divide the butter fat into a hard fat, a cocoa butter-like confectionary fat and an oil.

The filtrate from the crystallization described is returned to the crystallization vessel and the temperature is slowly lowered to 4-6 ° C in substantially the same manner as in the first crystallization. Without stirring, the process takes 6-12 hours, but 35 with stirring at 35-70 rpm. minute only two hours.

S DK 161771B

The precipitate is isolated in the same way as described above, and at this stage it is very important to wash the precipitate effectively. acetone which has cooled to approx. 2 ° C. Two washouts with an amount corresponding to approx. 10% of the original amount should be sufficient.

In this process a combination of decanting and switching and filtration can be used. The crystallizations described can also be done in a semi-continuous fashion. process using the appropriate storage tanks and the crystallization vessel, whereby the leaching may occur in circuits of first and second fractionation.

The butterfat fractionation can also be done by one of several methods for continuous fractionation. One such method is e.g. The Votator method which uses scraped surface crystallizers and short residence times. Equilibrium is achieved by incremental mixing in circulation, rather than by intense manipulation of long duration. This system includes a very efficient vertical centrifugal filter.

The confectionery industry uses millions of pounds of cocoa butter annually to make chocolate and other confectionery products.

20 Cocoa butter is the ideal confectionary fat because it is solid at room temperature but melts completely at body temperature. It is an agricultural product that is poorly produced, and for many years the industry has been searching for other fats to supplement this valuable product. Unfortunately, cocoa butter is polymorphic in crystalline properties, and when mixed with other fats, the mixture very often has a lower melting point than each of the ingredients of the mixture. If the melting point of the mixture is substantially lowered, the valuable melting characteristic of the cocoa butter is lost and the problem of gray coating on the chocolate occurs. In the past, milk fat has been mixed with cocoa butter in the manufacture of cream chocolate melting characteristics. The product that can be prepared by the process of this invention, namely, butterfat confectionery fat, is also made from milk fat (butterfat) and has a similar formula.

DK 161771 B

9 Consistency with cocoa butter. This compatibility is illustrated by the DSC thermograms of FIG. 2a and 2b. FIG. 2a shows the thermogram of a mixture of 50% cocoa butter with 50% butterfat confectionery fat (fraction P-2), while FIG. 2b shows the thermogram for pure cocoa butter. The two thermograms are very similar to each other 5.

Yet another advantage of the invention is the preservation of the highly valued butter odor and butter flavor in the individual fractions when prepared under reasonable conditions.

The invention will be described in more detail with reference to the following examples of practicing the method according to the invention:

Example 1

Fractionation of butterfat

A mixture of 1000 grams of butterfat and 7500 milliliters of acetone 15 (dissolution ratio 7.5 ml per gram of fat) is heated to approx.

45 ° C until all the butterfat has dissolved. The solution is transferred to a crystallizer and stirred slowly at 35-70 rpm. while the temperature of the solution is gradually lowered to 15 ° C over a period of 1 hour. Crystallization began at 20-22 ° C and became vigorous at 18 ° C. When the temperature reached 15 ° C, stirring was stopped and the mixture was kept at this temperature for an additional 15 minutes. During this period, fat crystals precipitated rapidly on the bottom of the crystallizer. The clear supernatant was removed with a siphon, using a weak vacuum. However, the crystals could also be isolated by vacuum filtration. The yield of crystals (P-1) was 80 grams and the DSC thermogram indicated the melting point of this fraction (P-1) to 53 ° C, see Figs. 1a.

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The overlying solution (F-1) was returned to the crystallizer, stirred at 35-70 rpm. stirring was continued at this temperature for 15 minutes, after which the mixture was kept for an additional 45 minutes at this temperature without stirring.

The fat crystals precipitated rapidly on the bottom of the crystallizer and the overlying solution was again removed with adherent under a weak vacuum. The remaining crystals were then washed twice with ca. 200 ml of cold acetone, which was cooled before approx. 2 ° C. The acetone was also removed with a swab. The yield of crystals (P-2) was approx. 150 grams after removal of the remaining acetone. The crystals needed only one washout with acetone if they were isolated by vacuum filtration. The DSC thermogram of the precipitated crystals (P-2) 15 was similar to the thermogram of cocoa butter, showing a rapid and sharp melting at 37-38 ° C, see fig. 1b.

The overlying filtrate (F-2), after removal of the acetone, yielded 770 grams of a pale yellow oil. The thermogram of F-2 is shown in FIG. 1c.

The fractionation steps and yields are illustrated in Table A. The fatty acid contents of a typical butterfat fraction (Example 1) are shown in Table B. The melting curves of the butterfat fractions are shown by the DSC thermograms of FIG. 1a, 1b and 1c, FIG. 1a shows the DSC thermogram of the high melting point P-1 fraction, FIG. 1b shows the DSC thermogram of the confectionery fat fraction P-2, and FIG. 1c shows the DSC thermogram for the oil fraction F-2. The compatibility of the butterfat confectionery fraction P-2 with cocoa butter is shown in FIG. 2a and 2b, FIG. 2a, the DSC shows the thermogram for a 50% / 50% mixture of cocoa butter and fraction P-2, while FIG. Figure 2b shows the DSC thermogram for pure cocoa butter. The thermogram of FIG. 2a is very similar to that of FIG. 2b.

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11

Table A

Fractionation steps and yields T000 grams of butterfat stirring at 35-70 rpm solvent: acetone crystallization time: 2 h dissolution ratio 7.5 to 1

crystallization temperature 14-16 ° C

precipitate P-1 filtrate F-1 yield 80 grams yield 920 grams> f stirring at 35 rpm solvent: acetone crystallization time 2 h dissolution ratio: same crystallization temperature

4-6 ° C

precipitate P-2 filtrate F-2 yield 150 grams yield 770 grams

Table B

Fatty acid content (% by weight) of butterfat and butterfat_

Sm8irfeat melting point) IniSSw "F-2 ° all C-4 to 8 6 1 3 8 C-10 3 1 2 3 C-12 2 2 3 3 C-14 10 11 9 10 G-14: 1 21 1 DK 161771 B j

12 I

i!

Table B (continued) ******* - ******., £££££) _ P1urefcag) ~ · E-2 611e C-15 2 2 3 2 5 C-16 27 40 37 27 C-16: 1 4 1 3 3 C-17 2 2 2 1 C-17: 1 1 1 - - C-18 11 26 20 9 10 C-18: 1 24 9 15 30 C-18: 2 3 1 1 2

Example 2

Palm oil fractions: 1000 grams of refined palm oil and 7500 milliliters of acetone (dissolution ratio 7.5 ml per gram of 10 fat) are mixed, heated and crystallized as in Example 1 at the fractionation steps listed in Table A. j i

dividends

Fraction Yield (% by weight) P-1 (high melting point) 10 15 P-2 (confectionery fat) 26 F-2 (oil) 64

Fatty acid content (% by weight)

Fatty Acid Palm Oil P-1 P-2 F-2 C-14 1 211 20 C-16 47 82 58 36 C-18 4 65 4 C-18: 1 38 10 32 46 C-18: 2 9 1 2 13

13 DK 161771 B

The physical properties of these fractions are found by differential scanning calorimetry (DSC) in the form of melting curves. The high melting point P-1 fraction is shown in FIG. 3, the confectionery fat fraction P-2 in FIG. 4, and the melting characteristic of the oil in FIG.

5 5. Although there is a great difference in the composition of butterfat and palm oil, the fractions formed by the process of the invention have uniform physical properties. This is seen by comparing the melting curves of the butterfat fractions in FIG. 1a, 1b and 1c with the melting curves of FIG. 3, 4 and 5 for the palm oil-10 fractions.

The invention can be used in many areas. It is e.g. It is known that short-chain fatty acids have bacteriological and antifungal properties. However, only some of the fat fractions possess these properties and, after isolation, these fractions will therefore be suitable for admixture in creams, lotions, ointments and emollients for both cosmetic and pharmaceutical use.

Claims (6)

A process for solution fractionation of animal or vegetable fats with a total content of saturated fatty acids of between 25-65%, especially butterfat and palm oil, in three well-defined fractions, the first fraction being a solid glyceride fraction. | a melting point above 45 ° C, the other a semi-solid glyceride fraction similar to cocoa butter with respect to 10 melting characteristics, the melting point of which is between 32-42 ° C, and the third fraction being an oil at room temperature, characterized in that the process consists of the following steps: a) dissolving the fat in a solvent, the solution ratio being from 1.5 to 7.5 ml per ml. g of fat and the solution is heated so much that complete solution is obtained, i.e. to approx. B) the solution of step a) is crystallized over a period of 1-12 hours by slow cooling to 14-16 ° C, 20 c) isolating a first precipitate formed in step b) which precipitate is the d) leaching of the first precipitate with a solvent cooled to a temperature at least 2 ° C lower than the crystallization temperature; e) crystallizing the filtrate from step c) i. 1-12 hours, slowly lowering the temperature to 4-6 ° C and dissolving ratio unchanged; f) isolating another precipitate formed in step 30 e), which second precipitate is a semi-solid glyceride fraction whose melting point g) leaching of the second precipitate with a solvent cooled to ca. And h) removing the solvent from the filtrate in step f) to obtain a third glyceride fraction which is an oil at room temperature. DK 161771 B Process according to claim 1, characterized in that the solvent is acetone. Process according to claim 1, characterized in that the solvent is methyl ethyl ketone or methyl isobutyl ketone. Process according to claim 1, characterized in that the solvent is methyl, ethyl or isopropyl alcohol. Process according to claim 1, characterized in that the solvent is 1- or 2-nitropropane. Process according to claim 1, characterized in that the solvent is an azeotropic hydrocarbon mixture having a boiling point of less than 130 ° C.